Xylene Isomerization Process and Catalyst Therefor

ABSTRACT

The invention concerns a xylenes isomerization process for the production of equilibrium or near-equilibrium xylenes. The process utilizes a catalyst comprising HZSM-5 or MCM-49 and process conditions including a temperature of less than 295° C. and a pressure sufficient to maintain the xylenes in liquid phase. In embodiments, the process can be operated in a continuous mode with ppm levels of dissolved H 2  in the feed and in other embodiments in a cyclic mode without the H 2  in feed but with periodic regenerations using a feed having low ppm levels of H 2 .

PRIORITY CLAIM

This application claims the benefit of U.S. Provisional Application No.61/326,445 filed Apr. 21, 2010, the disclosure of which is incorporatedherein by reference in its entirety.

FIELD OF THE INVENTION

The invention relates to a xylene isomerization process and catalysttherefor.

BACKGROUND OF THE INVENTION

An equilibrium mixture of xylenes contains about 24% para-xylene (PX),56% meta-xylene (MX), and 20% ortho-xylene (OX). PX is relatively highvalue as compared with MX and OX, and it is desirable to isomerize OXand/or MX to PX, such as isomerizing a PX-lean stream to equilibrium forPX recovery. It is an active area of research.

Typically xylene streams found in chemical or petrochemical plants alsocontain ethylbenzene (EB). Conventional isomerization technologiesoperating at high temperatures (e.g.: 400° C.) in vapor phase isomerizethe xylenes and dealkylate EB to benzene. Other vapor-phaseisomerization technologies convert EB to xylenes in addition to xylenesisomerization. There are also liquid-phase isomerization technologies.Conventional isomerization technologies typically produce significantamounts (>0.5 mol%) of byproducts such as benzene and A9+ (aromatichydrocarbons having 9 or more carbon atoms). Thus, it is necessary toinstall a topping and/or a tailing distillation column to reduce thebyproducts concentrations. In many situations, installing newdistillation columns would not be feasible due to economic and/orphysical constraints. Most isomerization technologies also require highhydrogen partial pressure to maintain the catalyst activity, which makesthe process arrangement complex and expensive.

U.S. Pat. No. 6,180,550 teaches ZSM-5 useful in the liquid phaseisomerization of xylene. The zeolite used has a SiO2/A1203 ratio of lessthan 20.

U.S. Pat. No. 6,448,459 teaches isomerization without hydrogen in aliquid phase diluted with toluene used as desorbent in a simulatedmoving bed adsorptive separation unit. The catalyst used in the liquidphase isomerization is said to be zeolitic, for example ZSM-5, and inthe example it is specified that there is no hydrogen.

U.S. Pat. No. 6,872,866 teaches a two stage, liquid or partially liquidphase isomerization process using a zeolitic-based catalyst systempreferably based on zeolite beta and on pentasil-type zeolite. Thispatent also sets forth numerous examples of prior art catalyst systems,including ZSM-5.

U.S. Pat. No. 7,244,409 teaches small crystallite ZSM-5 which may beused for isomerization reactions.

U.S. Pat. No. 7,371,913 teaches a ZSM-5 mole sieve further comprising Gais used as an isomerization catalyst to provide an increased amount ofPX in the liquid phase in the substantial absence of H₂. The amount ofH₂ present is stated to be less than 0.05, preferably less than 0.01,mole H₂/mole feed.

U.S. 7,495,137 teaches a two-stage isomerization system, the first zoneoperating in the absence of hydrogen (as in the above patent) using aplatinum-free catalyst and the second zone using a catalyst comprising amolecular sieve and a platinum-group metal component. The catalyst inthe first zone is preferably a Ga-MFI-type zeolite and it is preferredthat the catalyst for the first zone has a Si:Al ratio greater thanabout 10.

U.S. 7,592,499 teaches a multi-stage process for co-producing PX andstyrene from a feed of hydrocarbons comprising xylenes and EB. In thefirst stage, PX is separated from the feed by means of a simulatedmoving bed adsorptive separation column to produce a raffinatecomprising EB, OX, and MX. Next, EB in the raffinate is dehydrogenatedto styrene. Eventually a stream containing unconverted EB, MX, and OX isobtained and contacted with an isomerization catalyst to preferably inthe liquid phase. The catalyst is zeolitic, such as ZSM-5.

U.S. 2009-0182182 teaches a two-stage isomerization process, the firststage in the liquid phase in the substantial absence of H₂ to obtain anintermediate stream. In the second stage, the intermediate stream ismixed with a stream rich in naphthene, and contacted with anisomerization catalyst. By “substantial absence of H₂” is meant no freehydrogen is added to a feed mixture and any dissolved hydrogen fromprior processing is substantially less than about 0.05 moles/mole offeed. The first isomerization catalyst includes a molecular sieve,typically an aluminosilicate having a Si:Al₂ ratio greater than about10. In the example given, a Ga source is used to make the catalysts forboth the first and second isomerization steps.

U.S. Publication No. 2010-0152508 teaches a process for isomerizationthat is at least partially in the liquid phase and includes a step ofremoval of C9 aromatic hydrocarbons from a feedstream including C8 andC9 aromatic hydrocarbons.

The present inventors have discovered a xylenes isomerization technologyto provide a product enriched in PX when compared with the feedstream tothe process. In embodiments the process takes a PX-lean feedstream toproduce a product having equilibrium or near equilibrium xylenes. Inembodiments the process produces very low level of by-products (such as<0.3 wt. %). Thus there is no need for additional distillation columns.Furthermore, the technology can operate without the presence of anyhydrogen or with only low ppm levels of dissolved hydrogen, making it asimple and cost-effective process.

SUMMARY OF THE INVENTION

The invention is directed to a xylenes isomerization process, includinga liquid phase isomerization, for the production of equilibrium ornear-equilibrium xylenes, wherein the process conditions include atemperature of less than 295° C. and a pressure sufficient to maintainthe xylenes in liquid phase.

In embodiments, the liquid phase isomerization process utilizes acatalyst comprising ZSM-5 and/or MCM-49.

In embodiments, the process can be operated in a continuous mode withlow ppm levels of H₂ in the feed and in other embodiments in a cyclicmode without H₂ in feed but with periodic regenerations.

In embodiments, the process is operated in a continuous mode with from 4to 10 ppm H₂ at a temperature of less than 295° C. and total pressuresufficient to maintain the xylenes in the liquid phase.

In embodiments, the process is operated in a cyclic mode without H₂ inthe feed but with periodic regenerations using greater than 5 ppm H₂ inthe feed, in embodiments at least 10 ppm H₂ in the feed, in otherembodiments at least 20 ppm H₂ in the feed.

It is an object of the invention to provide a xylene isomerizationprocess including a liquid phase isomerization process which, comparedto conventional xylenes isomerization processes, provides at least oneof the advantages selected from low investment, low operating costs, lowbyproduct yields, and low xylene loss.

It is another object of the invention to provide a liquid phase xyleneisomerization process that uses at most only low ppm levels of hydrogenand that in embodiments can be regenerated numerous times by a verysimple in situ procedure.

These and other objects, features, and advantages will become apparentas reference is made to the following detailed description, preferredembodiments, examples, and appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A and 1B illustrate catalytic activities of ZSM-5 and MCM-49zeolites for embodiments of the liquid phase xylene isomerizationprocess according to the invention.

FIG. 2 illustrate the effect of a ZSM-5 zeolite's crystal size andsilica/alumina ratio for an embodiment of the liquid phase xyleneisomerization process according to the invention.

FIG. 3 illustrate the effect of an extrudate's zeolite content for anembodiment of the liquid phase xylene isomerization process according tothe invention.

DETAILED DESCRIPTION

According to the invention, there is provided a process for theisomerization of xylenes including the liquid phase isomerization ofxylenes at a temperature of less than 295° C. and a pressure sufficientto maintain the xylenes in liquid phase.

In embodiments, the process utilizes a catalyst comprising a zeolite,preferably at least one selected from the group consisting of ZSM-5 andMCM-49.

In embodiments, the process utilizes a catalyst comprising ZSM-5 alongwith a binder or the ZSM-5 may be self-bound.

In preferred embodiments the catalyst is characterized by one or more ofthe following characteristics:

the ZSM-5 is in the proton form (HZSM-5);

the ZSM-5 has a crystal size of less than 0.1 microns;

the ZSM-5 has a mesoporous surface area (MSA) greater than 45 m²/g;

the ZSM-5 has a zeolite surface area (ZSA) to mesoporous surface area(MSA) ratio of less than 9;

a silica to alumina weight ratio in the range of 20 to 50.

As used herein, “crystal size” means average crystal size and isconveniently determined by electron microscopy, as is well-known per sein the art. The surface areas may also be determined by methodswell-known in the art.

The catalyst can be formulated using various techniques such asextrusion, pelletization, oil dropping, spray drying, and the like,techniques which are per se well-known in the art. Optionally, bindermaterials such as alumina, silica, clay, aluminosilicate, may be used inthe formulation. In preferred embodiments, the catalyst is characterizedby one or more of the following properties with respect to the binder:

the zeolite:binder weight ratio is from 1:9 to 9:1;

the binder preferably comprises silica, alumina, and aluminosilicate;

the catalyst is preferably extruded using acetic acid as extrusion aid.

The preferred reactor is fixed bed and the flow may be up or down.

In embodiments, the process can be operated in a continuous mode withlow ppm levels of H₂ dissolved in the feed and in other embodiments in acyclic mode without the H₂ in feed but with periodic regenerations.

By “low ppm” is meant levels which one of ordinary skill in the artwould express as “ppm”, generally below 100 ppm. The expression “ppm” isweight ppm (wppm) unless otherwise specified.

In embodiments, very low level of by products are produced, such as lessthan 1 wt % or preferably less than 0.5 wt % of by products selectedfrom non-aromatic compounds, benzene and A9+ (aromatic hydrocarbonshaving 9 or more carbon atoms), and mixtures thereof.

The process comprises contacting a feedstream comprising C8 aromatichydrocarbons with a catalyst suitable for isomerization, preferably acatalyst comprising MCM-49 and/or ZSM-5, preferably a catalystcomprising ZSM-5 and more preferably having one or more of theaforementioned properties and most preferably all of the aforementionedproperties, at a temperature below 295° C., preferably below 280° C.,and at a pressure sufficiently to keep the reactant in liquid phase. Oneof skill in the art in the possession of the present disclosure would beable to determine other operating characteristics, such as a lowertemperature, within which the present invention may be practice. Lowerlimits may be, for instance, above 180° C. or 190° C. or 200° C., or210° C., and the like. The flow rate can be selected by one of ordinaryskill in the art in possession of the present disclosure, but mayadvantageously be selected within the range from 1 to 100 WHSV,preferably from 1 to 20 WHSV, and more preferably from 1 to 10 WHSV.

The following examples are intended to exemplify the invention and arenot intended to be limiting.

In an embodiment, a PX-lean xylenes feedstream is fed to at least onereactor. “PX-lean”, for the purposes of the present invention, meansless than equilibrium amount of paraxylene, i.e., less than 24 mol % PX,based on 100 mol % xylene feedstream. In preferred embodiments, thefeedstream will comprise from 2 to 18 mol % PX, based on 100 mol %xylene feedstream.

In preferred embodiments, there is no H₂ in the xylene feedstream. It isdifficult to measure H₂ in xylene feedstreams with any accuracy at lowppm levels (which may be attempted by such methods as GC techniquescommonly known), and therefore the expression “no H₂” as used herein ismeant no H₂ beyond inevitable impurities, and also that there is nopurposeful addition of H₂ in such feedstreams. The feedstreams may alsobe purged with an inert gas, such as N₂, to lower H₂ levels from“inevitable impurities” if so desired. The expression “H₂-free”, alsoused herein, is intended to mean the same thing as “no H₂”. Inembodiments, it will be sufficient for the purposes of the presentinvention that the “H₂-free” feedstream contain less than or equal to 4ppm H₂. Low ppm amounts of H₂ used in the continuous mode will be,preferably, greater than 4 ppm to about 10 ppm (equivalent to 0.00001moles of H₂ per mole of xylenes). However, the amount of H₂ may behigher, such as 50 or 100 ppm.

In practice, one way of accomplishing low ppm levels of H₂ is bycontrolling the quantity of H₂ added to the “H₂-free stream”. Forinstance, we may know that a stream is H₂ free because we know whatupstream processing it has gone through, such as distillation whichwould rid a stream of H2 easily. Then by carefully controlling how muchH₂ is added, we would know the final H₂ quantity.

The reactor may be of any type, such as a fixed bed reactor, fluid bedreactor, dense bed reactor, and the like. For example, the reactor couldbe a tubular fixed bed reactor packed with a catalyst suitable forisomerization of C8 aromatic hydrocarbons, more preferably a catalystcomprising HZSM-5 or MCM-49. The feedstream can flow through the reactorin either up-flow or down-flow mode. Such a reactor can be operated at atemperature below 295° C., a flow rate within the range of 0.1 to 100WHSV (Weight Hourly Space Velocity), and a pressure sufficiently high tokeep the feedstream at liquid phase inside the reactor andadvantageously maintained so as to achieve the low byproducts yields.The person of ordinary skill in the art, in possession of the presentdisclosure, can achieve such conditions without more than routineexperimentation. Once temperature is set, those skilled in the art candetermine what pressure to use to keep it in liquid phase based onxylenes VLE (vapor-liquid-equilibrium) data. By way of example, withoutintending to be limiting, in embodiments the pressure may be above 100psia, or preferably above 150 psia.

Depending on the operating conditions, the catalyst may exhibit a slowdeactivation. It has been also unexpectedly discovered by the presentinventors that low ppm levels of dissolved hydrogen in the xylenes feedcan completely mitigate such deactivation. Thus one can run the reactorwith a H₂-free xylene feed for a period of time, the length of whichdepends on the selection of operating parameters of the operator, and atthe end of the operation, replace the H₂-free xylene feed with aH₂-containing xylene feed at the same operating conditions. Thus, inthis embodiment, H₂ is now purposefully added to the feed. Only low ppmlevels are necessary. Although, as mentioned above, GC techniques arenot particularly good at measuring H₂ levels accurately at low ppmlevels in a C8 aromatic hydrocarbon feedstream, the presence of H₂ atsuch levels can be estimated based on H₂-xylenes VLE. For the purposesof the present invention, when the “H₂-free” feedstream is defined ascontaining 0.00005 moles H₂/mole xylenes or less, or 0.00001 molesH₂/mole xylenes or less, the H₂-containing xylene feed should havegreater than 0.00005 moles H₂/mole xylenes, or greater than 0.00001moles H₂/mole xylenes, respectively.

It has been surprisingly found that the H₂-containing xylene feed willregenerate the catalyst to recover the lost activity. The regenerationperiod can vary, such as from 1 day to a few weeks. At the end of theregeneration, an operator can replace the H₂-containing feed with theH₂-free feed and resume the normal operation.

This regeneration technique has at least several advantages. It is easyto implement and cost effective. Hydrogen can readily dissolve inxylenes at the required level. By way of example, at 160 psia, 71 ppm H₂will be dissolved in xylenes at room temperature. It does not requiresuch expensive and complex process equipment as separator andrecompressor that is required for the high H₂ partial pressure inconventional vapor-phase isomerization technologies. The regeneration isdone with a H₂-containing xylene feed at the same conditions as that forthe normal operation, which means that even during regeneration, thereactor is still producing equilibrium or near equilibrium xylenes; thuswould be no productivity loss. In embodiments the operator can increasethe H₂ concentration during the regeneration to as high as 100% H₂ and0% xylenes and still accomplish the objective.

In another embodiment, low ppm levels of H₂ such as 4 to 100 ppm,preferably 4 to 10 ppm (within the standard sampling error possible bycurrent measurement techniques) are dissolved in the xylene feed and fedto the reactor continuously through out the operation. The H₂ at suchlevels will completely prevent the catalyst deactivation. As a result,in this embodiment, there is provided a process allowing for long,continuous operation without any need to stop for regeneration. Inaddition to the advantages listed above, in this embodiment aconsistently high PX yield is possible at all times.

In order to better understand the invention, reference will now be madeto specific examples, which are intended to merely be representative ofthe present invention and should not be taken as limiting.

EXAMPLE 1

A sample of 1/16″ extruded H-ZSM-5 catalyst, obtained from PQCorporation, having a silica/alumina ratio of 30, was ground to 30/60mesh and packed in an 0.180″ID×0.625″ length tubular reactor to a levelof 0.13 gram. The catalyst was then dried under flowing nitrogen gas at200° C. for 10 hours to remove moisture. Afterward, the catalyst wascontacted with xylenes feed, first without dissolved H₂ (H₂-freeaccording to the present invention), and then with H₂ dissolved in thefeed to a level of 130 ppm by weight. Isomerization conditions were setat 280 psia, 232° C. and 3 WHSV. Under these conditions, the xylenesfeed was isomerized and the rate of catalyst deactivation orregeneration was calculated based on product analysis.

Results, as shown in the Table 1, demonstrate that the presence ofdissolved hydrogen not only stopped catalyst deactivation but alsorestored and maintain the catalyst activity.

TABLE 1 Xylene Feed without dissolved H₂ with dissolved H₂ Change in PXyield (wt %) −1.0 +0.7 Cumulative bed weights of 0-1996 1996-3910 feed(g of feed/g of catalyst) Rate of deactivation −5.0 × 10⁻⁴ (ΔPX wt %/bedweights) Rate of restoration +4.0 × 10⁻⁴ (ΔPX wt %/bed weights)

Additional experiments were performed in order to identify the scope ofthe present invention, wherein a PX-lean feedstream is isomerized toequilibrium while minimizing byproduct formation.

Preliminary experiments were performed on ZSM-5 zeolites with varyingproperties and on a MCM-49 zeolite as listed in Table 2.

TABLE 2 Crystal Crystal Type SiO2/Al2O3 Ratios Crystal Sizes, micron IZSM-5 25 0.5 II ZSM-5 60 <0.1 III ZSM-5 25 <0.1 IV MCM-49

EXAMPLE 2

This example illustrates that the unexpected findings with respect tothe process of the invention may be achieved by catalysts othercatalysts.

MCM49 and ZSM5 zeolites (shown in Table 3) were tested for liquid phasexylene isomerization according to the invention. The feeds used areshown in Table 4, with results shown in FIG. 1. Both zeolites isomerizedxylenes to para-xylenes at 236° C., 3 weighted hourly space velocity (1gram of catalyst used), and 265 psig. MCM49 had a higher para-xyleneyield but also higher by-products as indicated by the product C9+content, also shown in FIG. 1. Thus, one could choose either zeolite forliquid phase xylene isomerization on a case-by-case basis.

TABLE 3 Catalyst Crystal Form Tested Finishing A III powder Exchangedand Calcined for 6 hours at 1000 F. B IV Self-Bound Exchanged andCalcined for 8 1/16″ Quadrulobe hours at 1000 F. (extruded with PVA)

TABLE 4 Feed wt % for Feed wt % for Feed Component Catalyst A Catalyst BMethylcyclohexane 0.84 0.01 DiMethylcyclohexane 1.93 4.10 Benzene 0.000.005 Toluene 1.32 1.00 Ethylbenzene 2.86 3.06 Para Xylene 13.36 12.80Meta Xylene 62.90 62.26 Ortho Xylene 16.77 16.75 Cumene 0.02 0.02 OtherC9+ 0.01 0.01

EXAMPLE 3

The present inventors have also discovered that silica/alumina ratio andcrystal size of the HZSM-5 zeolite are important factors to the catalystperformance. Thus for liquid phase xylenes isomerization according tothe present invention, a catalyst based on a HZSM-5 zeolite withsilica/alumina ratio of 30 or less and crystal size less than 0.1 micronprovides even more advantageous liquid phase xylenes isomerizationperformance, superior to that of the catalysts with ZSM-5 zeoliteshaving silica/alumina ratios and crystal sizes outside the specifiedranges.

Three ZSM-5 extrudates were prepared using 3 different ZSM5 crystals andare shown in Table 5. The crystals were ion exchanged to proton form andextruded into 1/20″ quadrulobes extrudates with an alumina binder and 1%acetic acid as an extrusion aide. The weight ratio of crystal to binderwas 4. The extrudates were calcined at 1000° F.

TABLE 5 Reactor Flowrate, Catalyst temp. Reactor Weight Hourly CatalystCrystal loading, g ° C. pressure, psig Space Velocity C I 0.4550 246 2653.69 D II 0.4545 246 265 3.69 E III 0.4610 246 265 3.74

The extrudates were evaluated using a feed of 13.28% para-xylene, 63.72%meta-xylene, 17.94% ortho-xylene, 1.52% ethylbenzene, 1.28% toluene, and2.25% non-aromatics, and low levels of benzene and nine-carbon aromaticcompounds. The tests were performed in a ¼″ stainless steel reactor withthe feed going up flow through the catalyst bed. Test conditions arelisted in Table 4.

Test results are shown in FIG. 2. It is seen that all three catalystswere able to isomerize meta- and ortho-xylene to para-xylene. However,the PX yield decreased in the order of E>C>D and that the catalyst withcrystal III delivered a near-equilibrium para-xylene yield (97-98%equilibrium). A comparison between Catalysts E and D shows that loweringsilica/alumina ratio from 60 to 25 raised para-xylene yield from about20.2% to about 22.2% and between Catalysts E and C shows that reducingcrystal size from 0.5 to <0.1 micron raised para-xylene yield from anaverage of 21.6% to 22.2%.

EXAMPLES 4-6

In preparing formed extrudates, higher ratios of zeolite to binderproved to more efficiently isomerize the xylenes to para-xylene.

Three ZSM-5 extrudates were prepared all using crystal III (described inTable 2) and are shown in Table 6. The crystals were ion exchanged toproton form and extruded into 1/20″ quadrulobes extrudates with analumina binder. Catalyst H was also extruded using 1% acetic acid as anextrusion aide to improve crush strength. All extrudates were calcinedat 1000° F. (about 538° C.).

TABLE 6 Catalyst Crystal Zeolite:Binder F III 65:35 G III 75:25 H III80:20

The extrudates were evaluated using a feed shown in Table 7. One gram ofeach catalyst was used in the testing. The pressure was 265 psig for allruns and the feed was H₂-free PX-lean xylenes.

TABLE 7 Feed Component Wt % C8 non-Aromatics 4.31 Benzene 0.004 Toluene0.99 Ethylbenzene 3.07 Para Xylene 12.79 Meta Xylene 62.1 Ortho Xylene16.71 C9 0.01 C10+ 0.02

Test results are shown in FIG. 3 and Table 8. For Example 3, catalysts Fand H were both tested at 246° C. and WHSV based on only the zeolite of4.6. Overall WHSVs were 3.0 for Catalyst F and 3.7 for Catalyst H.Despite the higher overall WHSV, Catalyst H yielded higher para-xyleneconcentration in the product. This trend was also observed in Examples 5and 6. Therefore, increasing the zeolite concentration in the formedextrudate makes the zeolite more effective.

TABLE 8 p-Xylene Cumulative product Overall Zeolite Feed/ concen- Temp.,WHSV, WHSV, Catalyst tration Catalyst C. 1/hr 1/h (g/g) (wt %) Exam- F246 3.0 4.6 500 20.9 ple 3 H 246 3.7 4.6 500 21.2 Exam- F 250 3.0 4.61000 21.0 ple 4 G 250 3.5 4.67 1000 21.3 Exam- F 254 3.0 4.6 1700 21.2ple 5 H 255 3.7 4.6 1700 21.6

While the illustrative embodiments of the invention have been describedwith particularity, it will be understood that various othermodifications will be apparent to and can be readily made by thoseskilled in the art without departing from the spirit and scope of theinvention.

Trade names used herein are indicated by a ™ symbol or ® symbol,indicating that the names may be protected by certain trademark rights,e.g., they may be registered trademarks in various jurisdictions. Allpatents and patent applications, test procedures (such as ASTM methods,UL methods, and the like), and other documents cited herein are fullyincorporated by reference to the extent such disclosure is notinconsistent with this invention and for all jurisdictions in which suchincorporation is permitted. When numerical lower limits and numericalupper limits are listed herein, ranges from any lower limit to any upperlimit are contemplated.

1. -17. (canceled)
 18. A catalyst comprising H-ZSM-5, furthercharacterized by at least one of the following characteristics: anaverage crystal size of less than 0.1 microns; a mesoporous surface area(MSA) greater than 45 m²/g; a zeolite surface area (ZSA) to mesoporoussurface area (MSA) ratio of less than 9; and optionally comprising abinder.
 19. The catalyst of claim 18, further comprising a binderselected from at least one of alumina, silica, clay, andaluminosilicate.
 20. The catalyst of claim 19, in contact with afeedstream comprising C8 aromatic hydrocarbons and from 4 to 10 ppmlevels of H₂, in a reactor at a temperature below 295° C.
 21. Thecatalyst of claim 18, wherein said catalyst has a silica to aluminaweight ratio (as SiO₂:Al₂O₃) of from 20 to
 50. 22. The catalyst of claim19, wherein said binder is in the amount of 10 - 90 wt % based on theweight of said catalyst.
 23. The catalyst of claim 18, wherein saidcatalyst is formed by a method selected from extrusion, pelletization,oil dropping, or spray drying, using at least one extrusion aid selectedfrom acetic acid.
 24. The catalyst of claim 18, having all of thefollowing characteristics: an average crystal size of less than 0.1microns; a mesoporous surface area (MSA) greater than 45 m²/g; and azeolite surface area (ZSA) to mesoporous surface area (MSA) ratio ofless than 9.